United States Patent Application: 0140130415

We remind you that New York City's Columbia University, as seen for just the most recent example in our report of:

Columbia University Converts CO2 to Ethylene | Research & Development | News; concerning: "United States Patent Application 20130048506 - Electrodes for High Efficiency Aqueous Reduction of CO2; 2013; Inventor: Ed Chen, NY; Assignee: The Trustees of Columbia University in the City of New York; Abstract: An electrolytic cell system to convert carbon dioxide to a hydrocarbon that includes a first electrode including a substrate having a metal porous dendritic structure applied thereon; a second electrode, and an electrical input adapted for coupling to a source of electricity, for applying a voltage across the first electrode and the second electrode. ... Claims: An electrolytic cell system to convert carbon dioxide to a hydrocarbon comprising: (a) a first electrode including a substrate having a metal porous dendritic structure applied thereon; (b) a second electrode; and (c) an electrical input adapted for coupling to a source of electricity, for applying a voltage across the first electrode and the second electrode. ... The electrolytic cell system ... wherein at least one of the first electrode and the second electrode is at least partially saturated with carbon dioxide (and) further comprising a membrane to dissolve carbon dioxide in the electrolyte (and) further comprising a conduit to pass carbon dioxide directly to the surface of the first electrode. ... A method of converting carbon dioxide to a hydrocarbon comprising: providing an electrolytic cell that includes (a) a first electrode including a substrate having a metal porous dendritic structure applied thereon; (b) a second electrode, and (c) an electrical input adapted for coupling to a source of electricity, for applying a voltage across the first electrode and the second electrode; introducing a source of carbon dioxide to the electrolytic cell; and applying the voltage across the first electrode and the second electrode. ... The method ... wherein the carbon dioxide is obtained from an air stream, a combustion exhaust stream, or a pre-existing carbon dioxide source. The method ... wherein the hydrocarbon (produced) is ethylene";

 

has been lately at work advancing and refining technology, like that seen in our report of: 
Chicago Converts CO2 into Methane and Ethylene | Research & Development | News; concerning: "United States Patent 4,897,167 - Electrochemical Reduction of CO2 to CH4 (Methane) and C2H4 (Ethylene);1990; Assignee: Gas Research Institute, Chicago; Abstract: A process for electrochemical reduction of CO2 to CH4 and C2H4 providing both high current densities and high Faradaic efficiencies. The process is carried out in an electrochemical cell wherein copper is electrodeposited in situ on the cathode surface making freshly deposited copper available for the electrochemical reduction. Faradaic efficiencies of about 75 to about 98 percent for production of CH4 (Methane) and C2H4 (Ethylene) are obtained";
which began to be established some decades ago, wherein electrolytic processes are employed to effect the conversion of Carbon Dioxide, along with Hydrogen concurently extracted from the Water, H2O, molecule, almost directly into simple hydrocarbons like Methane and Ethylene.
Also more lately, various entities, like the USDOE, as seen in:
USDOE Idaho Lab Recycles More CO2 | Research & Development | News; concerning:"Model of High Temperature H2O/CO2 Co-electrolysis; 2007;By: G. Hawkes, J. O'Brien, C. Stoots, Stephen Herring, Joe Hartvigsen; Research Organization: Idaho National Laboratory (INL); Sponsoring Organization: USDOE; Abstract: A three-dimensional computational fluid dynamics (CFD) model has been created to model high temperature co-electrolysis of steam and carbon dioxide in a planar solid oxide electrolyzer (SOE) using solid oxide fuel cell technology. A research program is under way at the Idaho National Laboratory (INL) to simultaneously address the research and scale-up issues associated with the implementation of planar solid-oxide electrolysis cell technology for syngas production from CO2 and steam. ... A strong interest exists in the large-scale production of syngas from CO2 and steam to be reformed into a usable transportation fuel. With the price of oil currently around $60 / barrel, synthetically-derived hydrocarbon fuels (synfuels) have become economical. Synfuels are typically produced from syngas – hydrogen (H2) and carbon monoxide (CO) -- using the Fischer-Tropsch process, discovered by Germany before World War II. Syngas (can)  be produced via separate electrolysis of steam and CO2. There are, however, significant advantages to electrolyzing steam and CO2 simultaneously. Focusing only upon the electrolysis step, co-electrolysis is more energy-efficient than separate electrolysis";
and the USDOE's contractors, as in:
Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development | News; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; Inventors: Joseph Hartvigsen, et. al., Utah; Assignee: Ceramatec, Inc., Salt Lake City; Abstract: A method is provided for synthesizing synthesis gas from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water using a sodium-conducting electrochemical cell. Synthesis gas is also produced by the coelectrolysis of carbon dioxide and steam in a solid oxide fuel cell or solid oxide electrolytic cell. The synthesis gas produced may then be further processed and eventually converted into a liquid fuel suitable for transportation or other applications";
have been developing the technology to, in instead of directly synthesizing hydrocarbons from CO2 and H2O, via a catalyzed electrolytic process, break Carbon Dioxide and Water together down into their simpler constituents, Carbon Monoxide, Hydrogen and Oxygen, with the CO and H2 comprising a "syngas" which can be chemically, catalytically condensed, as via the "Fischer-Tropsch process", into "liquid fuel".
But, Columbia University - - in addition to, as in our above-cited report concerning "United States Patent Application 20130048506 - Electrodes for High Efficiency Aqueous Reduction of CO2", developing the technology for the electrolytic conversion of CO2 and H2O directly into simple hydrocarbons - - has, as well, been focusing attention on strictly thermo-chemical processes for the decomposition of Carbon Dioxide and Water, to form blends of Carbon Monoxide and Hydrogen "syngas", like that discussed in our report of:

USDOE Solar Thermochemical CO2-to-Fuel | Research & Development | News; concerning: "Solar Fuel Production Through The Thermochemical Decomposition of Carbon Dioxide; Nathan P. Siegel, et. al.,  Sandia National Laboratories, Albuquerque, NM USA; Abstract: Solar energy systems based on an intermittent resource benefit from an energy storage mechanism that decouples the solar resource from the load, enabling operation when the resource is unavailable. For utility scale power plants this is achieved with thermal energy storage (TES) systems incorporating significant volumes (some larger than 106 liters) of inorganic salts. Storing solar energy in the form of chemical fuels offers another more energy dense storage mechanism that enables the utilization of solar energy to address the energy needs of the transportation sector. Concentrating solar power (CSP) systems are capable of operating at the elevated temperatures needed to drive thermochemical reactions that convert the stable combustion products, carbon dioxide and water, first into synthesis gas, a mixture of carbon monoxide and hydrogen, and then into liquid hydrocarbon fuels such as methanol, gasoline, and jet fuel. Sandia National Laboratories (SNL) is developing a process called Sunshine to Petrol, or S2P, in which a two-step thermochemical cycle is used to produce synthesis gas via H2O and/or CO2 decomposition that may then be converted into a liquid hydrocarbon fuel".

And, there might in such strictly "thermochemical" processes be some synergies which could be achieved by combining such thermo-chemical reforming of CO2 and H2O with other carbon conversion and fuel synthesis processes.
As we attempt to point out in comment following, and nserted within, excerpts from the initial link in this dispatch to: 
"United States Patent Application 20140130415 - Method and System for Production of Hydrogen and Carbon Monoxide
Abstract: A method for preparing a fuel using oxygen-storing compound nanoparticles is provided, in which the nanoparticles is heated at a first temperature to release an amount of oxygen, thereby producing a reduced oxide compound, and the reduced oxide compound is exposed to a gas at a second temperature to produce the fuel. The gas can include carbon dioxide and water vapor, and the fuel can include carbon monoxide and/or hydrogen. The oxygen-storing compound nanoparticles can be nano ceria or nano ceria doped with one or more metals, such as Cu (Copper) and/or Zr (Zirconium). A system for carrying out the method is also disclosed.
Claims: A method for preparing a fuel from an oxygen-storing compound in the form of nanoparticles, comprising: heating the nanoparticles at a first temperature to release an amount of oxygen, thereby producing a reduced oxide compound; and exposing the reduced oxide compound to a gas at a second temperature to produce the fuel, wherein the gas is selected from the group consisting of carbon dioxide and water vapor.
The method ... further comprising selecting the second temperature to be less than the first temperature (and) further comprising selecting the first temperature to be about 700 C. or lower (and) further comprising selecting the first temperature to be about 150 C to about 300 C.
The method ... wherein the fuel comprises at least one of carbon monoxide and molecular hydrogen.
The method ... wherein the oxygen-storing compound comprises cerium oxide.
(The above "cerium oxide", or Cerium compounds in general, are apparently effective Oxygen mediators in these sorts of reactions. We remind you of much earlier, similar thermo-chemical CO2-recycling work established with Cerium and Cerium compounds by our US Department of Energy, as in our report of:

USDOE Hydrocarbon Syngas from CO2 and H2O | Research & Development | News; concerning: "United States Patent 4,313,925 - Thermochemical Cyclic System for Decomposing H2O and/or CO2 by Means of Cerium-Titanium-Sodium-Oxygen Compounds; 1982; Inventor: Carlos Bamberger, Oak Ridge, TN; Assignee: The USA as Represented by the USDOE; Abstract: A thermochemical closed cyclic process for the decomposition of water and/or carbon dioxide to hydrogen and/or carbon monoxide begins with the reaction of ceric oxide (CeO2), titanium dioxide (TiO2) and sodium titanate (Na2TiO3) to form sodium cerous titanate (NaCeTi2O6) and oxygen. Sodium cerous titanate (NaCeTi2O6) reacted with sodium carbonate (Na2CO3) in the presence of steam, produces hydrogen. The same reaction, in the absence of steam, produces carbon monoxide. The products, ceric oxide and sodium titanate, obtained in either case, are treated with carbon dioxide and water to produce ceric oxide, titanium dioxide, sodium titanate, and sodium bicarbonate. After dissolving sodium bicarbonate from the mixture in water, the remaining insoluble compounds are used as starting materials for a subsequent cycle. The sodium bicarbonate can be converted to sodium carbonate by heating and returned to the cycle. ... A method for producing hydrogen comprising reacting sodium cerous titanate, sodium carbonate and steam at a temperature above 500C to produce ceric oxide, sodium titanate, carbon dioxide and hydrogen. (Again, some Carbon Dioxide is generated, and recycled, within the system itself.) ... An object of any thermochemical process is the direct use of heat from an energy producing facility requiring no fossil fuels, e.g., a ...solar source. It is a further object of this invention to provide a novel cyclic thermochemical process for splitting water into hydrogen and oxygen. In addition, this invention provides a novel thermochemical route for the production of carbon monoxide";

wherein heat, thermal energy alone is specified to drive the process of breaking CO2 and H2O down into their simpler constituents. The more recent technologies, as in our subject, "United States Patent Application 20140130415 - Method and System for Production of Hydrogen and Carbon Monoxide", utilize more sophisticated catalysis, with an overall reduced demand for energy, in processes that are, compared to the related, earlier USDOE processes, like the above "United States Patent 4,313,925 - Thermochemical Cyclic System for Decomposing H2O and/or CO2 by Means of Cerium-Titanium-Sodium-Oxygen Compounds", much simpler in terms of the chemical reaction sequences employed. Overall, the newer processes, such as the one developed herein by Columbia University, are much more efficient.)

The method ... wherein the oxygen-storing compound comprises cerium oxide doped with a transition metal or an oxide thereof (and) wherein the oxygen-storing compound comprises a cerium oxide doped with a rare earth metal or an oxide thereof (and) wherein the transition metal comprises a metal selected from the group consisting of Copper, Zirconium, and Palladium (and) wherein the transition metal comprises a metal selected from the group consisting of Hafnium, Iron, Cobalt, Chromium, Zinc, Nickel, Gold, Titanium, Platinum, Rhodium, and Ruthenium.

The method ... wherein the transition metal comprises Copper such that Cu replaces about 5% to about 10% of cerium in the cerium oxide.

The method ... wherein the average size of the nanoparticles of the oxygen-storing compound is about 2 to about 15 nanometers.

A system for preparing a fuel using nanoparticles of an oxygen-storing compound and a gas selected from the group consisting of carbon dioxide and water vapor, comprising: a reactor adapted to receive nanoparticles of the oxygen-storing compound in a predetermined location therein and the gas through a gas intake; a heater adapted to heat the oxygen-storing nanoparticles to a first temperature to reduce the nanoparticles to form a reduced oxygen-storing compound; wherein the gas intake is positioned to deliver the gas to contact the reduced oxygen-storing compound at a second temperature, thereby converting at least a portion of the gas to the fuel.

The system ... wherein the fuel comprises at least one of carbon monoxide and molecular hydrogen.

The system ... wherein the heater is configured to deliver heat having a maximum temperature of about 450 C (and) wherein the heater is coupled with a heat source having a maximum temperature of about 450 C or lower (and) wherein the heat source is waste heat from an industrial process (or) wherein the heater is coupled with a solar concentration device.

The system ... wherein the oxygen-storing compound comprises cerium oxide doped with a transition metal or an oxide thereof (and) wherein the transition metal comprises a metal selected from the group consisting of Cu, Zr, and Pd.

The system ... further comprising a support structure having at least one flow channel having a gas-permeable wall, the oxygen-storing nanoparticles loaded on the support structure.

Background: Converting H2O and CO2 gases into syngas (H2 and CO) can be a useful strategy for carbon sequestration and as a source of renewable energy.

One technique for realizing energy conversion involves heating porous monolithic cerium dioxide (ceria) to about 1600 C to release oxygen from the micron-sized (bulk) crystals/grains. When the resulting reduced ceria is cooled, H2O or CO2 can be converted to H2 and CO, respectively, while ceria is re-oxidized and ready for another thermal-gas cycle. This high reduction temperature of about 1600 C is dictated by the reduction thermodynamics of bulk ceria (i.e. ceria grains in micron-size and larger). However, the high temperature can increase the cost of the process and reduce material lifetime. Therefore, it is desirable to lower the ceria reduction temperature to improve the economics and material stability of the process.

Summary and Description: The disclosed subject matter provides techniques for preparing a fuel using an oxygen-storing compound. In accordance with one aspect of the disclosed subject matter, methods of preparing a fuel using an oxygen-storing compound in the form of nanoparticles is provided. An exemplary method includes heating the nanoparticles at a first temperature to release an amount of oxygen, thus producing a reduced oxide compound, and exposing the reduced oxide compound to gaseous carbon dioxide and/or water vapor at a second temperature to produce CO and/or H2, which are also referred as the gaseous fuel, or fuel.

The heater can be coupled with a heat source, which can be waste heat from an industrial process or facility, for example, ... power plants.
The waste heat from these sources can have various grades (i.e. different maximum temperatures). The heat source can also include a solar concentration device or other heat generation devices.
(The immediately above "solar concentration device" would be as in the USDOE's above-cited "Sunshine to Petrol" development effort. Solar is the method preferred, obviously, by Columbia, to provide the thermal energy to power the chemical reduction, the "de-oxidation", as it were, of the Cerium Oxide, and is emphasized throughout. Many options exist to drive that reduction, however, so that the Cerium again becomes available to chemically reduce CO2 and H2O into Carbon Monoxide and Hydrogen. One option might be that the oxidized Ceria, after having converted CO2 and H2O into "syngas", and binding to Oxygen in that step, could be used as an "oxygen donor", in a process like that seen in our report of:

"Coal Gasification Using the ZnO/Zn Redox System; Energy & Fuels; 1996; Research Center for Carbon Recycling and Utilization, Tokyo Institute of Technology, Japan; Laboratory for Energy and Process Technology, Paul Scherrer Institute, Switzerland; (and,) Mechanical Engineering Department, Valparaiso University, Indiana; A two-step thermochemical process is proposed for converting coal to high-quality synthesis gas. In the first, high temperature, endothermic step, coal is reacted with zinc oxide to form metallic zinc and an H2-CO gas mixture. In the second, low temperature, exothermic step, zinc is used for splitting water and producing hydrogen and zinc oxide. The hydrogen is employed to enrich and adjust the synthesis gas mixture obtained in the first step, while the zinc oxide is recycled to the first step. Experimental studies have shown a more effective chemical conversion obtained via the proposed two-step scheme as compared to that obtained via the conventional single-step direct steam gasification".

We some time ago made other reports concerning such metal oxide cyclic "Redox" processes for gasifying Coal, to produce hydrocarbon synthesis gas, but the above reference describes it most concisely. We'll revisit the topic in future reports, since those technologies offer the potential of dramatically reducing the co-production of Carbon Dioxide in the Coal gasification process, thus making that process itself inherently more efficient and productive.)

As liquid fuels such as gasoline and diesel oil can be prepared from CO and H2, the mixture of CO and H2 is also referred as syngas
The Fischer-Tropsch process can convert molecular hydrogen and carbon monoxide into alkane fuels ... .

Both coal and biomass can be used as feedstocks for this process (but, the) metal-oxide thermochemical cycle (as disclosed herein) can eliminate the need for such feedstocks because it can produce the necessary reactants directly from carbon dioxide gas and water vapor.

The high temperatures used for the reduction of ceria can be achieved by solar means such as the solar generation device heat source. 

The waste heat from these sources can have various grades (i.e. different maximum temperatures). The heat source can also include a solar concentration device or other heat generation devices.

When fossil fuels are burned, carbon dioxide and water can be released.

The Fischer-Tropsch process can convert molecular hydrogen and carbon monoxide into alkane fuels .., ,

Both coal and biomass can be used as feedstocks for this process in non-ideal conditions. The metal-oxide thermochemical cycle can eliminate the need for such feedstocks because it can produce the necessary reactants directly from carbon dioxide gas and water vapor".

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Our thoughts here are that the use of "coal", as above, as a feedstock specifically for this process, would be "non-ideal" only because it would represent an unnecessary consumption of Coal, our largest and most reliable source of electric power, when the by-product of generating electricity with Coal, Carbon Dioxide, can be used instead.

Further, although, as Columbia specifies, the "heater can be coupled with a heat source, which can be waste heat from an industrial process or facility, for example, ... power plants", and even though the heat energy requirements are reduced in this process relative to earlier, related examples of the concept, such "waste heat" would still unlikely be sufficient enough to satisfy the requirements of the process, and would probably need to be supplemented with "a solar concentration device or other heat generation devices".

So, we don't really know how suitable the process of our subject, "United States Patent Application 20140130415 - Method and System for Production of Hydrogen and Carbon Monoxide", would actually be coupled to one or more of our Coal-fired power plants in often-cloudy old Coal Country, unless some other form of environmental energy in the form of heat, or readily convertible into heat, could be accessed.

It, thus, might not have as much applicability in Coal Country as an electrochemical process for converting Carbon Dioxide and Water into hydrocarbon synthesis gas, like that disclosed in the earlier-cited "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; Inventors: Joseph Hartvigsen, et. al., Utah; Assignee: Ceramatec, Inc., Salt Lake City; Abstract: A method is provided for synthesizing synthesis gas from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water", or Columbia University's own "United States Patent Application 20130048506 - Electrodes for High Efficiency Aqueous Reduction of CO2", which results directly in the formation of simple hydrocarbons as opposed to hydrocarbon synthesis gas.

But, as seen in our report of:

Columbia University Practical Extraction of Atmospheric CO2 | Research & Development | News; concerning: "United States Patent 8,246,731 - Systems and Methods for Extraction of Carbon Dioxide from Air; 2012; Inventors: Klaus Lackner and Frank Zeman, NY; Assignee: The Trustees of Columbia University in the City of New York; Abstract: The present invention describes methods and systems for extracting, capturing, reducing, storing, sequestering, or disposing of carbon dioxide (CO2), particularly from the air. The CO2 extraction methods and systems involve the use of chemical processes. Methods are also described for extracting and/or capturing CO2 via exposing air containing carbon dioxide to a solution comprising a base - - resulting in a basic solution which absorbs carbon dioxide and produces a carbonate solution. The solution is causticized and the temperature is increased to release carbon dioxide, followed by hydration of solid components to regenerate the base";

Columbia University has, as well, developed and refined the technology for extracting the needed Carbon Dioxide from the air itself. So, the entire CO2 collection and conversion to syngas system could be constructed someplace with abundant solar energy - -, say Florida, which would give all us Appalachian Coal people something to go have a look at, a Carbon Dioxide-to-Gasoline factory, during our vacations. During which vacations we might be more inclined to drive somewhere, like the beach, knowing that the Gasoline we were burning was being made in the USA, out of a much-maligned raw material, Carbon Dioxide, that some folks want to shut down our Coal-fired power plants for co-producing a little of.

Carbon Dioxide can be seen and treated as a valuable raw material resource. And, the sooner everyone wakes up to that fact, and starts to demand that we act on that fact, the better off everyone in Coal Country, and everyone else  in the entire United States of America, will be.

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